Printing cellulosic textile materials



Patented Oct. 15, 1940 UNITED STATES PATENT OFFICE PRINTING CELLULOSIC TEXTILE MATERIALS Denys Percival Milbum, Blackley, Manchester,

England, assignor to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application March 8, 1938, Serial No. 194,703. In Great Britain March 10, 1937 6 Claims.

R-NCO where R is an aliphatic hydrocarbon radical having not less than 12 carbon atoms.

The so-printed material is then dried and heated as by steaming for a short time and is then dyed, conveniently by padding; finally, the ground colour having been developed if necessary, the material is washed, soaped and dried in the usual way.

It will be understood that when the printing paste contains only the resisting agent, together with the usual thickeners, for example, gum senegal, gum tragacanth or British gum, and assistants, for example, emulsifying agents, such as sulphated fatty alcohols, there are produced,

finally, white patterns on a coloured ground.

Alternatively the printing paste may contain,

in addition to the resist agent and other ingre dients, an ice colour preparation which is capable of being developed by treatmentwith acid. In this case, the steaming operation to which, after printing and drying, the fabric is subjected, is modified in that it is carried out in the presence of the vapour of a suitable acid, for example, formic acid or acetic acid. In this ,way there are finally produced coloured patterns on a differently coloured ground.

As dyestufi's for providing theground colour, l-

using cold padding liquors and drying the fabric after padding by means of hot air rather than by passing it over heated cylinders. It is believed that the success of the process depends upon the production, during the steaming operation, of temporarily water-repellent areas on the fabric where the printing paste has been applied. Such water-repellency would be impaired or destroyed by working at elevated temperatures.

Padding is preferably done through the nip so as to minimise the time of contact of the fabric with the padding liquor.

Where the resist agent is an isocyanate it is conveniently employed in the form of an aqueous emulsion or suspension which may be produced, if desired, with the aid of an emulisfying agent such, for example, as a sulphated fatty alcohol.

As compounds of formula RNCO suitable to be used in the process of the invention there may be mentioned, for example, dodecyl, tridecyl, tetradecyl, pentadecyl, cetyl, heptadecyl, octadecyl, eikosyl and octadecenyl isocyanates, likewise mixtures of isocyanates such as may be obtained from the mixed amines derived from the mixed Cotton fabric is printed with a paste made by incorporating together Parts Heptadecyl isocyanate 4 Sodium cetyl sulphate 0.2 Starch-tragacanth thickening 1:1 50 Water--- 45.8

The printed fabric is dried, steamed for 15 minutes and then grounded by padding in one of the following solutions:

Soledon Jade Green XS paste (the sulphuric ester of leuco dimethoxydibenzanthrone) Soledon Orange R powder (Schultz Farbstofitabellen, 7th edtn. N o. 1349) Tragacanth thickening 1:1 5 5 Sodium nitrite 30% aqueous solution 3 3 Water 89 90. 5

It is then dried, developed by passing through a 2% solution of sulphuric acid (168 Tw.) at C., washed, soaped and dried. There is thus obtained a clear-cut white pattern on either a green or an orange ground.

Example 2 Cotton fabric is printed and steamed as in Potassium carbonate Example 1. It is then grounded by padding in one of the following solutions:

Parts Parts Caledon Jade Green paste (Colour Index No. 1101) Caledon Blue 3G paste (Colour Index No. 1109)-.. 2 Tragacanth thickening 1:1 5 5 Sodium formaldehyde sulphoxylate g The grounded print is dried, steamed for 10 min-' utes, oxidised in the usual manner to develop the ground colour, soaped at the boil and again dried. There is thus obtained a clear-cut white pattern on either a green or ablue ground.

Example 3 Cotton fabric is printed andsteamed as in Example 1 and then padded with the following;

Parts A blue dyestuif which is the sodium salt of 1- sulphohydroxydimethylfuchson dicarboxylic acid (Colour Index No. 722) 1 Acetate of chrome liquor 28 Tw '7 Tragacanth thickening 1:1 5 Water 87 The grounded print is steamed for --1 hour, washed, soaped and dried. A clear-cut white pattern on a blue ground is thus obtained.

Example 4 Cotton fabric is printed and steamed as in Example 1 and is then padded with one of the following solutions:

An azoic dyestufl printing preparation as com- Parts mercially supplied, comprising a mixture of a diazoimino compound of diazotised 4-chloro-otoluidine and the o-toluidide of 2:3-hydroxynaphthoic acid An amic dyestuff printing preparation as commercially supplied, comprising a diazoimino compound from diazotised 4-benzoylamino-2z5- diethoxyaniline mixed with the anilide of 2:3- hydroxy-naphthoic acid Caustic soda aqueous solution 76 Tw Tragacanth thickening 1:1 5

Water 93.3 9

NOINH It is then dried, steamedfor 15 minutes in the presence of acetic and formic acid vapours, washed, soaped at the boil and dried. There is thus obtained a clear-cut white pattern on either a red or a blue ground.

Example 5 Cotton fabric is printed and steamed as in Example 1 and is padded in the following liquor:

A is heated until the dyestuff is completely vatted; it is then cooled and B is added to it.

After padding, the material is exposed to the air for minute to develop the dyestuff, then washed, chromed, soaped at the boil and dried. There is obtained a clear-cut white pattern on a green ground.

Example 6 The following mixtures P and Q are made up separately by warming the ingredients together until all is dissolved:

Parts An azoic dyestuif printing preparation, as commercially supplied, comprising a mixture of a diazoimino compound of diazotised 4-chloroo-toluidine and the o-phenetidide of 2:3-hydroxynaphthoic acid 7 An azoic dyestuif printing preparation, as comniercially supphed, comprising a mixture of a dlazolm no compound of diazotised 4-chloroo-tolnldine and the o-toluidide of 2:3-hydroxynaphthoic acid 7 Methylated spirit 3 3 Aqueous sodium hydroxide 76 'lw 3 3 Starch-tragacanth thickening (1:1). 50 50 Water l5 l5 P and Q are then cooled and mixed together to form a printing paste. Cotton fabric is printed with one of the printing pastes A and B. It is then dried and steamed for 15 minutes in the presence of acetic and formic acid vapoursv The printed fabric is then grounded by padding in one of the following liquors, solution A being used on material printed with paste A and solution B on material printed with paste B:

Soledon Jade Green XS paste (the sulphuric ester of leuco dimethoxy dibenzantbrone) A blue dyestutf which is the sulphuric ester of leuco 16:174liethylene ether of dihydroxydibonzanthrone in the form of a 20% aqueous paste" Tragacanth thickening (1:1) Sodium nitrite 30% aqueous solution. Water It is then dried, preferably by hot air, and developed by passage through a 2% aqueous solution of sulphuric acid (168 Tw.) at 70 C. It is finally washed, soaped at the boil and dried. There is thus obtained a clear-cut scarlet pattern on a green ground and a clear-cut red pattern on a blue ground.

Example 7 Cotton fabric is printed and steamed as in Example 6. It is-then grounded by padding with the following liquor:

Parts An azoic dyestufi printing preparation as commercially supplied, comprising a mixture of a diazoimino compound of diazotised 4-' benzoylamino-2:S-diethoxyaniline and the anilide of 2:3-hydroxynphthoic acid 2 Aqueous sodium hydroxide 76 TW 3 Tragacanth thickening (1:1) 5 Water It is then dried and steamed in the presence of acetic and formic acid vapours for A to /2 hour.

The material is finally soaped at the boil and dried. There is thus obtained a clear-cut scarlet or red pattern on a blue ground.

Example 8 Cotton fabric is printed and steamed as in Example 6. It is then grounded by padding in the following liquor:

- Parts A blue dyestuif which. is the sodium salt of 1- sulphohydroxydimethylfuchson dicarboxylic acid 1 Aqueous acetate of chrome solution 28 Tw 7 Tragacanth thickening (1:1) 5 Water 87 The printed and grounded fabric is then steamed for to 1 hour, soaped and dried. There is thus obtained a clear-cut scarlet or red pattern on a blue ground.

Example 9 Cotton fabric is printed and steamed as in Example 6. It is then grounded by padding in the following liquor:

- Parts Fast Printing Green S (Colour Index No. 2) 2 Water 89 Tragacanth thickening (1:1) 5 Aqueous ferrous sulphate 21 Tw 4 Cotton fabric is printed and steamed as in Example 6. It is then grounded by padding in the following liquor:

In making thissolution the first three ingredients are heated with 30 parts of water until the dyestufi is completely vatted. The solution is then cooled and the remaining 64 parts of water are added.

After grounding the material is exposed to the air for minute to develop the ground colour and is then washed, chromed, soaped at the boil and dried. There is obtained a clear-cut scarlet or red pattern on a green ground.

If in the above examples theheptadecylisocyanate is replaced by an equal weight of hexadecyl isocyanate or octadecylisocyanate, similar excellent resists are obtained.

The above examples deal only with the application of the process to cotton fabric, but it is to be understood that it can be applied also to other cellulosic material, e. g., viscose rayon and also to fabrics constituted in part of other textile fibres, for example certain cotton-wool, viscosewool or viscose-pure silk unions.

I claim:

1. A process of printing cellulosic textile materials in resist styles to produce patterns on a colored ground which comprises applying to the celluiosic textile material a resist printing paste which contains as the active resist agent an allphatic isocyanate having the general formula, RNCO, where R is an aliphatic hydrocarbon radical containing 12 or more carbon atoms, drying the material, steaming the material, and then dyeing it to produce a ground shade.

2. A- process as claimed in claim 1 wherein the printing paste also contains an ice color preparation capable of being developed by acid.

3. A process as claimed in claim 1 wherein the dyestuif which is used to produce the ground shade is applied by padding.

4. A process as claimed in claim 1 wherein the dyestufi used to provide the ground shade is sclected from the group consisting of vat dyestuffs, azoic colors, and mordant dyestuffs.

5. A process of coloring cellulosic fabric in predetermined designs, which comprises printing upon the same in predetermined designs a resist paste comprising as active resist an alkyl isocyanate wherein the alkyl group contains not less than 12 carbon atoms; drying the printed fabric, steaming the dried fabric to develop a temporary water-repellent efiect in the printed areas, then padding the fabric with a developable ground color, and further treating the same to develop the ground color.

6. A process as set forth in claim 5 wherein heptadecyl isocyanate is used as the active resist agent in the resist printing paste.

DENYS PERCIVAL MILBURN. 

